In comparison with polymers containing long per-fluoroalkyl chains (CnF2n+1, n >= 8), perfluoropolyalkyl ethers (PFPEs) have been demonstrated to be environmentally friendly polymeric materials. Thus, PFPEs are expected to be alternatives to long perfluoroalkyl chain polymers. However, due to the poor solubility in common organic solvents they are generally prepared and used in fluorinated solvents, which can also cause harmful impacts on the environment. Therefore, it is urgent to explore a strategy for the preparation of high-performance PFPE polymers using environmentally friendly solvents. In this study, three kinds of novel methacrylate macromers bearing PFPE chains with low molar mass were designed and synthesized. The PFPE polymer coatings on polycarbonate plates were obtained by a combinational strategy of spin-coating and in situ photopolymerization of the macromers under UV irradiation. The results indicated that the polymer coatings could be prepared in nonfluorinated solvents, such as 2-propanol. Then the surface properties of the polymer coatings were investigated. It was found that the surface properties of the polymer coatings were related to the structures of the polymers. When CONH-C6H4 as a spacer was incorporated between the backbone and the PFPE chain, the hydrophobicity and oleophobicity of the polymer coatings were significantly enhanced, which is attributed to hydrogen bonds and pi-pi interaction between the PFPE chains. It is obvious that the synergetic effect of hydrogen bonds and pi-pi interaction can facilitate the PFPE chains to form a more stable fluorine-rich surface of the polymer coatings. Therefore, synthesis of a high-performance PFPE polymer has been successfully achieved based on PFPEs using an environmentally friendly solvent.